Piezoelectric material, piezoelectric element, and electronic equipment

ABSTRACT

There is provided a lead- and potassium-free piezoelectric material having a high piezoelectric constant and a satisfactory insulation property and a piezoelectric element that includes the piezoelectric material. The piezoelectric material contains a perovskite-type metal oxide having the general formula (1): (NaxBa1-y)(NbyTi1-y)O3 (wherein x satisfies 0.80≤x≤0.95, and y satisfies 0.85≤y≤0.95); and at least one rare-earth element selected from La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, wherein the rare-earth element content is more than 0 mol % and 5 mol % or less of the amount of perovskite-type metal oxide. The piezoelectric element includes the piezoelectric material.

This application is a continuation of U.S. application Ser. No.14/764,121, filed Jul. 28, 2015, which is a National Stage filing ofInternational Application No. PCT/JP2014/052186 filed Jan. 24, 2014,which claims the benefit of Japanese Patent Application No. 2013-014613,filed Jan. 29, 2013, each of which is hereby incorporated by referenceherein in their entirety.

TECHNICAL FIELD

The present invention relates to a piezoelectric material and moreparticularly to a lead-free piezoelectric material. The presentinvention also relates to a piezoelectric element, a multilayeredpiezoelectric element, a liquid discharge head, a liquid dischargeapparatus, an ultrasonic motor, an optical apparatus, a vibratoryapparatus, a dust removing device, an image pickup apparatus, andelectronic equipment, each including the piezoelectric material.

BACKGROUND ART

In general, piezoelectric ceramics are ABO₃ perovskite-type metaloxides, such as lead zirconate titanate (hereinafter referred to as“PZT”). However, PZT contains lead as an A site element, and its effecton the environment is regarded as a problem. Thus, there is a demand forpiezoelectric ceramics of lead-free perovskite-type metal oxides.

NPL 1 discloses that, in a solid solution of a small amount of bariumtitanate in an antiferroelectric material sodium niobate, sodium niobateconverts into a ferroelectric material. NPL 1 also discloses theremanent polarization, coercive field, piezoelectric constant, andelectromechanical coupling coefficient of a compound having a bariumtitanate concentration in the range of 5% to 20% sintered at atemperature in the range of 1200° C. to 1280° C. The material describedin NPL 1 is free of lead and potassium. Potassium is responsible forpoor sinterability and low moisture resistance. The Curie temperature ofthe material described in NPL 1 is higher than the Curie temperature(110° C. to 120° C.) of a typical lead-free piezoelectric materialbarium titanate. NPL 1 discloses that the Curie temperature of thecomposition (Na_(0.9)Ba_(0.1))(Nb_(0.9)Ti_(0.1))O₃ having the maximumpiezoelectric constant d₃₃=143 pC/N is 230° C.

PTL 1 discloses that the addition of cobalt to a piezoelectric ceramicthat is a solid solution of sodium niobate and barium titanate(NN—BT-Co) improves the piezoelectric constant. It is also disclosedthat a sample of the piezoelectric materials described in PTL 1 wasdifficult to polarize because of a low insulation resistance as low asapproximately 10⁶Ω.

CITATION LIST Patent Literature

-   PTL 1 Japanese Patent Laid-Open No. 2009-227535

Non Patent Literature

-   NPL 1 J. T. Zeng et. al., Journal of the American Ceramic Society,    2006, vol. 89, pp. 2828-2832

SUMMARY OF INVENTION Technical Problem

However, known piezoelectric materials that are solid solutions ofbarium titanate in sodium niobate (hereinafter referred to as NN—BT)unfortunately have insufficient piezoelectric performance. Because ofits poor insulation property, NN—BT-Co is difficult to polarize and haslimited application to piezoelectric elements.

The present invention solves such problems and provides a lead- andpotassium-free piezoelectric material having a high piezoelectricconstant and a satisfactory insulation property. The present inventionalso provides a piezoelectric element, a multilayered piezoelectricelement, a liquid discharge head, a liquid discharge apparatus, anultrasonic motor, an optical apparatus, a vibratory apparatus, a dustremoving device, an image pickup apparatus, and electronic equipment,each including the piezoelectric material.

Solution to Problem

A piezoelectric material according to one aspect of the presentinvention that solve the problems described above contains aperovskite-type metal oxide having the following general formula (1),and at least one rare-earth element selected from La, Pr, Nd, Pm, Sm,Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, wherein the rare-earth elementcontent is more than 0 mol % and 5 mol % or less of the amount ofperovskite-type metal oxide.

(Na_(x)Ba_(1-y))(Nb_(y)Ti_(1-y))O₃  (1)

(wherein x satisfies 0.80≤x≤0.95, and y satisfies 0.85≤y≤0.95)

A piezoelectric element according to one aspect of the present inventionincludes a first electrode, a piezoelectric material portion, and asecond electrode, wherein the piezoelectric material portion includesthe piezoelectric material described above.

A multilayered piezoelectric element according to one aspect of thepresent invention includes piezoelectric material layers and electrodelayers alternately stacked on top of one another. The electrode layersinclude an internal electrode. The piezoelectric material layers includethe piezoelectric material described above.

A liquid discharge head according to one aspect of the present inventionincludes a liquid chamber and a discharge port in communication with theliquid chamber. The liquid chamber has a vibrating portion that includesthe piezoelectric element or the multilayered piezoelectric elementdescribed above.

A liquid discharge apparatus according to one aspect of the presentinvention includes a stage configured to receive an object and theliquid discharge head described above.

An ultrasonic motor according to one aspect of the present inventionincludes a vibrating member and a moving body in contact with thevibrating member. The vibrating member includes the piezoelectricelement or the multilayered piezoelectric element described above.

An optical apparatus according to one aspect of the present inventionincludes a drive unit that includes the ultrasonic motor describedabove.

A vibratory apparatus according to one aspect of the present inventionincludes a vibrating member that includes the piezoelectric element orthe multilayered piezoelectric element described above.

A dust removing device according to one aspect of the present inventionincludes a vibrating portion including the vibratory apparatus describedabove.

An image pickup apparatus according to one aspect of the presentinvention includes the dust removing device described above and an imagepickup element unit, wherein the dust removing device includes avibrating component on a light-receiving surface side of the imagepickup element unit.

Electronic equipment according to one aspect of the present inventionincludes a piezoelectric acoustic component that includes thepiezoelectric element or the multilayered piezoelectric elementdescribed above.

Advantageous Effects of Invention

The present invention can provide a lead- and potassium-freepiezoelectric material having a high piezoelectric constant and asatisfactory insulation property. The present invention can also providea piezoelectric element, a multilayered piezoelectric element, a liquiddischarge head, a liquid discharge apparatus, an ultrasonic motor, anoptical apparatus, a vibratory apparatus, a dust removing device, animage pickup apparatus, and electronic equipment, each including thepiezoelectric material. A piezoelectric material according to anembodiment of the present invention contains no lead and has a lowenvironmental load. A piezoelectric material according to an embodimentof the present invention also contains no potassium and therefore hassatisfactory sinterability and moisture resistance.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic view of a piezoelectric element according to anembodiment of the present invention.

FIGS. 2A and 2B are schematic cross-sectional views of a multilayeredpiezoelectric element according to an embodiment of the presentinvention.

FIGS. 3A and 3B are schematic views of a liquid discharge head accordingto an embodiment of the present invention.

FIG. 4 is a schematic view of a liquid discharge apparatus according toan embodiment of the present invention.

FIG. 5 is a schematic view of a liquid discharge apparatus according toan embodiment of the present invention.

FIGS. 6A and 6B are schematic views of an ultrasonic motor according toan embodiment of the present invention.

FIGS. 7A and 7B are schematic views of an optical apparatus according toan embodiment of the present invention.

FIG. 8 is a schematic view of an optical apparatus according to anembodiment of the present invention.

FIGS. 9A and 9B are schematic views of a dust removing device includinga vibratory apparatus according to an embodiment of the presentinvention.

FIGS. 10A to 10C are schematic views of a piezoelectric element of adust removing device according to an embodiment of the presentinvention.

FIGS. 11A and 11B are schematic views illustrating the vibrationprinciple of a dust removing device according to an embodiment of thepresent invention.

FIG. 12 is a schematic view of an image pickup apparatus according to anembodiment of the present invention.

FIG. 13 is a schematic view of an image pickup apparatus according to anembodiment of the present invention.

FIG. 14 is a schematic view of electronic equipment according to anembodiment of the present invention.

DESCRIPTION OF EMBODIMENTS

Embodiments of the present invention will be described below.

The present invention provides a lead- and potassium-free piezoelectricmaterial based on a solid solution of barium titanate in sodium niobate(NN—BT) and having a high piezoelectric constant and a satisfactoryinsulation property. Utilizing its dielectric characteristics, apiezoelectric material according to an embodiment of the presentinvention can be used in various applications, such as capacitors,memories, and sensors.

A piezoelectric material according to an embodiment of the presentinvention contains a perovskite-type metal oxide having the followinggeneral formula (1) and at least one rare-earth element selected fromLa, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, wherein therare-earth element content is more than 0 mol % and 5 mol % or less ofthe amount of perovskite-type metal oxide.

(Na_(x)Ba_(1-y))(Nb_(y)Ti_(1-y))O₃  (1)

(wherein x satisfies 0.80≤x≤0.95, and y satisfies 0.85≤y≤0.95)

The term “perovskite-type metal oxide”, as used herein, refers to ametal oxide having a perovskite-type structure, which is ideally a cubicstructure, as described in Iwanami Rikagaku Jiten, 5th edition (IwanamiShoten, published on Feb. 20, 1998). A metal oxide having aperovskite-type structure is generally represented by the chemicalformula ABO₃. In a perovskite-type metal oxide, elements A and B in theform of ions occupy particular positions of a unit cell referred to asthe A site and the B site, respectively. For a cubic unit cell, theelement A occupies the vertexes of the cube, and the element B occupiesthe body-centered position of the cube. The element O as an oxygen anionoccupies the face-centered positions of the cube.

In the perovskite-type metal oxide having the general formula (1), themetallic elements at the A site are Na and Ba, and the metallic elementsat the B site are Nb and Ti. Na and Ba may partly occupy the B site.Likewise, Nb and Ti may partly occupy the A site.

In the general formula (1), although the molar ratio of the B siteelement to the element O is 1:3, small variations in the molar ratio(for example, 1.00:2.94 to 1.00:3.06) are within the scope of thepresent invention, provided that the metal oxide has the perovskite-typestructure as the primary phase. The perovskite-type structure of themetal oxide can be determined by structural analysis using X-raydiffraction or electron diffraction.

A piezoelectric material according to an embodiment of the presentinvention may have any form, such as a ceramic, powder, single crystal,membrane, or slurry, and may be a ceramic. The term “ceramic”, as usedherein, refers to an aggregate of crystal grains (also referred to as abulk), that is, a polycrystalline material, containing a metal oxide asthe base component and sintered by heat treatment. The term “ceramic”also includes a ceramic processed after sintering.

The value x of the general formula (1), which represents the abundanceof Na at the A site, may be in the range of 0.80≤x≤0.95. A value x ofless than 0.80 results in a deficiency of Na relative to Nb and theformation of an impurity phase (a phase having a similar X-raydiffraction pattern to that of Ba₄Nb₂O₉, Ba₆Ti₇Nb₉O₄₂, Ba₃Nb₄Ti₄O₂₁, orBa₃Nb_(3.2)Ti₅O₂₁). Metal oxide samples rich in such an impurity phasehave a low resistivity in the range of 10⁷ to 10⁸ Ω·cm and are difficultto polarize. A value x of more than 0.95 results in low piezoelectricityat room temperature. When x satisfies 0.80≤x≤0.95, the impurity phaserarely occurs, and the piezoelectric material has high piezoelectricity.The value x may be in the range of 0.80≤x≤0.93.

The value y of the general formula (1), which represents the abundanceof Nb at the B site, may be in the range of 0.85≤y≤0.95. A value y ofless than 0.85 results in a Curie temperature of less than 140° C. Avalue y of more than 0.95 results in low piezoelectricity at roomtemperature.

A value y in the range of 0.85≤y≤0.95 results in a Curie temperature of140° C. or more and high piezoelectricity.

A value y in the range of 0.85≤y≤0.90 results in a Curie temperature inthe range of approximately 90° C. to 230° C., which makes polarizationtreatment easy. A value y in the range of 0.88≤y≤0.90 results in a Curietemperature in the range of approximately 150° C. to 230° C., whichmakes polarization treatment easy and results in a low possibility ofdegradation of piezoelectric performance due to heat in a devicemanufacturing process.

The Curie temperature is a temperature above which the piezoelectricityof a piezoelectric material disappears. The term “Curie temperature”, asused herein, refers to a temperature at which the dielectric constant ishighest in the vicinity of the phase transition temperature between aferroelectric phase and a paraelectric phase. A perovskite-type metaloxide according to an embodiment of the present invention has asuccessive phase transition temperature in a temperature range lowerthan the Curie temperature. At the successive phase transitiontemperature, successive phase transition occurs from a tetragonalcrystal ferroelectric phase to an orthorhombic crystal ferroelectricphase. The relative dielectric constant is highest or has an inflectionpoint at the successive phase transition temperature. Thus, in the samemanner as in the Curie temperature, the successive phase transitiontemperature can be determined from the temperature dependence of therelative dielectric constant. For example, a solid solution0.9NaNbO₃-0.1BaTiO₃ makes a phase transition from an orthorhombiccrystal to a tetragonal crystal and to a cubic crystal with an increasein temperature.

The piezoelectric performance is highest in the vicinity of thesuccessive phase transition temperature. Thus, in the drivingtemperature range of the device (for example, −30° C. to 60° C.), whenthere is a need for consistent piezoelectric performance that isindependent of the temperature, it is desirable that no successive phasetransition exist in the driving temperature range. The dielectric lossas well as the piezoelectric performance depends on the temperature.

A piezoelectric material according to an embodiment of the presentinvention contains at least one rare-earth element (RE) selected fromLa, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Theseelements are rare-earth elements, and their trivalent ions are stable.

The rare-earth element content of a piezoelectric material according toan embodiment of the present invention is more than 0 mol % and 5 mol %or less, preferably more than 0 mol % and 3 mol % or less, of the amountof perovskite-type metal oxide. The rare-earth element content expressedin mol % is the molar ratio of the rare-earth element. A piezoelectricmaterial according to an embodiment of the present invention thatcontains 5 mol % or less rare-earth element has a high insulationresistance and a small low-temperature dielectric loss. This is probablybecause the rare-earth element mainly occupies the A site andcompensates for A site defects due to Na deficiency. This is alsoprobably because the successive phase transition temperature shifts to alower temperature, which reduces the low-temperature dielectric loss.The term “low temperature”, as used herein, refers to 0° C. or less.Thus, a device including a piezoelectric material according to anembodiment of the present invention can have an excellent piezoelectricproperty also at 0° C. or less.

A piezoelectric material according to an embodiment of the presentinvention has a satisfactory insulation property because 5 mol % or lessrare-earth element suppresses the reduction of Ti in firing in areducing atmosphere.

Among rare-earth elements, Lu, Yb, Er, Ho, and Dy can shift thesuccessive phase transition temperature to a lower temperature. La, Nd,Sm, and Dy can improve piezoelectricity at room temperature. However,the rare-earth element content of more than 5 mol % results in lowpiezoelectricity at room temperature.

The rare-earth element may be disposed on the A site or the B site orboth or in ceramic grain boundaries. The rare-earth element on the Asite can compensate for A site defects due to Na deficiency. Thedistribution of the rare-earth element in a sample and the occupationsite in a crystal can be determined with an electron microscope, byenergy dispersive X-ray spectroscopy, by X-ray diffraction, by Ramanscattering, or with a transmission electron microscope.

A piezoelectric material according to an embodiment of the presentinvention may contain the perovskite-type metal oxide, the rare-earthelement, and Cu. The Cu content is more than 0 mol % and 2 mol % orless, preferably 1 mol % or less, of the amount of perovskite-type metaloxide. The Cu content expressed in mol % is the molar ratio of Cu on ametal basis. The Cu content of 2 mol % or less in a piezoelectricmaterial according to an embodiment of the present invention can resultin increased resistivity, piezoelectric constant, and relative density.The term “relative density”, as used herein, refers to the ratio of themeasured density to the theoretical density. The theoretical density canbe calculated from the molecular weight and the lattice constant of thematerial, for example. The measured density can be measured usingArchimedes' principle, for example.

The firing temperature may be decreased. The sintering temperature isthe minimum firing temperature at which a sintered body having arelative density of 95% or more can be formed. Cu can reduce the pinningof spontaneous polarization in a piezoelectric material according to anembodiment of the present invention. Reduction of pinning makes it easyto change spontaneous polarization in the same direction throughpolarization treatment. This increases the impedance phase differencebetween resonance and non-resonance and increases the mechanical qualityfactor Qm. Because of its low melting point, Cu promotes liquid phasesintering. Thus, Cu may segregate in grain boundaries. Improvement ofliquid phase sintering reduces the number of pores in the sintered bodyand increases the density of the sintered body. A reduction in thenumber of pores results in an increased mechanical quality factor Qm.

Cu may be disposed on the A site or the B site or both or in ceramicgrain boundaries.

Sintering of crystals containing sodium niobate as a component may causethe evaporation or diffusion of Na, and the sample composition aftersintering may lack Na relative to Nb. Thus, the A site has defects.However, weighing an excessive amount of Na raw powder may result in apoor insulation property of the sintered body. Thus, part of added Cumay compensate for the defects on the A site. The raw materials may beweighed such that the Na deficiency is not more than 5% relative to Nbin the composition after firing, and Cu may be added to the rawmaterials.

When the Cu content of the perovskite-type metal oxide is more than 2mol %, this may result in the occurrence of an impurity phase and lowpiezoelectricity.

A piezoelectric material according to an embodiment of the presentinvention may satisfy x<y in the general formula (1). A deficiency of Barelative to Ti is unfavorable because it accelerates abnormal graingrowth. Even if Cu occupies the Ba site, the effect described abovecannot be produced because Cu has the same valence as Ba. Under thecondition of x<y, Cu is taken in the crystal lattice as a donor and caneasily produce its effect. The starting materials may have such acomposition that x is less than y. When x is greater than or equal to y,the sample has a very poor insulation property.

In order to facilitate the production of a piezoelectric materialaccording to an embodiment of the present invention or modify thephysical properties of a piezoelectric material according to anembodiment of the present invention, Ba may be partly substituted by adivalent metallic element, such as Sr or Ca. Likewise, 20 mol % or lessof Nb may be substituted by a pentavalent metallic element, such as Taor V. Likewise, 20 mol % or less of Ti may be substituted by Zr or Sn,or 15 mol % or less of Na may be substituted by Li. Likewise, at leastone element selected from Mn, Ni, and Zn may be added to theperovskite-type metal oxide having the general formula (1), wherein theat least one element constitutes 5 mol % or less of the perovskite-typemetal oxide. Likewise, 0.001 parts by weight or more and 4.000 parts byweight or less on a metal basis of an auxiliary component containing atleast one selected from Si and B may be added to 100 parts by weight ofthe piezoelectric material.

In order to form a ceramic (sintered body) of a piezoelectric materialaccording to an embodiment of the present invention, it is necessary toprepare a green compact. The green compact is a shaped solid of the rawpowder. The raw powder may be of high purity. The compact can be formedby uniaxial pressing, cold hydrostatic pressing, hot hydrostaticpressing, casting, or extrusion molding. The compact may be formed froma granulated powder. Sintering of the compact formed from a granulatedpowder has an advantage that the grain size distribution of the sinteredbody tends to become uniform.

The raw material powder of a piezoelectric material may be granulated byany method. Spray drying can make the particle size of the granulatedpowder more uniform.

A binder for use in granulation may be poly(vinyl alcohol) (PVA),poly(vinyl butyral) (PVB), or an acrylic resin. The amount of binder ispreferably in the range of 1 to 10 parts by weight per 100 parts byweight of the raw material powder of the piezoelectric material, morepreferably 2 to 5 parts by weight in order to increase the compactdensity.

The compact may be sintered by any method. Examples of the sinteringmethod include sintering in an electric furnace, sintering in a gasfurnace, electric heating, microwave sintering, millimeter-wavesintering, and hot isostatic pressing (HIP). Sintering in an electricfurnace or a gas furnace may be performed in a continuous furnace or abatch furnace.

The sintering temperature in the sintering method is not particularlylimited and may be a temperature at which the compounds can react tosufficiently grow crystals. The sintering temperature is preferably1050° C. or more and 1300° C. or less, more preferably 1100° C. or moreand 1200° C. or less, such that the grain size is in the range of 1 to10 μm. A piezoelectric material sintered in the temperature rangedescribed above has satisfactory piezoelectric performance. In order toensure the reproducibility and stability of the characteristics of apiezoelectric material produced by sintering, sintering may be performedat a constant temperature within the range described above for 2 hoursor more and 48 hours or less. Although two-step sintering may also beperformed, a sintering method without an abrupt temperature change canimprove productivity.

A piezoelectric material produced by sintering may be polished and thenheat-treated at the Curie temperature or higher. Heat treatment of thepiezoelectric material at the Curie temperature or higher can relievethe residual stress of the piezoelectric material resulting frommechanically polishing and thereby improves the piezoelectric propertyof the piezoelectric material. The heat-treatment time may be, but isnot limited to, one hour or more.

A piezoelectric material according to an embodiment of the presentinvention having a crystal grain size of more than 100 μm may have aninsufficient strength in a cutting process and a polishing processing.An average grain size of less than 0.3 μm results in lowpiezoelectricity. Thus, the average grain size may be 0.3 μm or more and100 μm or less.

It is desirable that when a piezoelectric material according to anembodiment of the present invention is used as a film formed on asubstrate the thickness of the piezoelectric material be 200 nm or moreand 10 μm or less, preferably 300 nm or more and 3 μm or less. When thepiezoelectric material film thickness is 200 nm or more and 10 μm orless, the piezoelectric element has a sufficient electromechanicalconversion function.

The film may be formed by any method, for example, a chemical solutiondeposition method (a CSD method), a sol-gel method, a metal-organicchemical vapor deposition method (a MOCVD method), a sputtering method,a pulsed laser deposition method (a PLD method), a hydrothermalsynthesis method, or an aerosol deposition method (an AD method). Thefilm may be formed by a chemical solution deposition method or asputtering method. The area of the film can easily be increased usingthe chemical solution deposition method or the sputtering method. Thesubstrate used for a piezoelectric material according to an embodimentof the present invention may be a single-crystal substrate having apolished (001) or (110) section. Use of such a single-crystal substratehaving a particular polished crystal face allows the piezoelectricmaterial film formed on the substrate surface to be strongly oriented inthe same direction.

(Piezoelectric Element)

A piezoelectric element manufactured using a piezoelectric materialaccording to an embodiment of the present invention will be describedbelow.

FIG. 1 is a schematic view of a piezoelectric element according to anembodiment of the present invention. The piezoelectric element includesa first electrode 1, a piezoelectric material portion 2, and a secondelectrode 3. The piezoelectric material of the piezoelectric materialportion 2 is a piezoelectric material according to an embodiment of thepresent invention.

The piezoelectric property of the piezoelectric material can beevaluated by at least attaching the first electrode 1 and the secondelectrode 3 to the piezoelectric material portion 2 to form thepiezoelectric element. Each of the first electrode 1 and the secondelectrode 3 is an electrically conductive layer having a thickness inthe range of approximately 5 nm to 10 μm. The material of each of thefirst electrode 1 and the second electrode 3 is not particularly limitedand may be any material that is commonly used for piezoelectricelements. Examples of such materials include metals, such as Ti, Pt, Ta,Ir, Sr, In, Sn, Au, Al, Fe, Cr, Ni, Pd, Ag, and Cu, and compoundsthereof.

Each of the first electrode 1 and the second electrode 3 may be made ofone of these materials or may be a multilayer made of two or more of thematerials. The material(s) of the first electrode 1 may be differentfrom the material(s) of the second electrode 3.

The first electrode 1 and the second electrode 3 may be manufactured byany method, for example, by baking a metal paste or using a sputteringprocess or a vapor deposition method. The first electrode 1 and thesecond electrode 3 may have a desired pattern.

The piezoelectric element may have a unidirectional polarization axis.Having the unidirectional polarization axis can increase thepiezoelectric constant of the piezoelectric element.

The polarization method for the piezoelectric element is notparticularly limited. Polarization treatment may be performed in theambient atmosphere or in an oil. The polarization temperature may be inthe range of 60° C. to 160° C. The optimum conditions for polarizationmay vary with the composition of the piezoelectric material of thepiezoelectric element. The electric field for the polarization treatmentmay be greater than or equal to the coercive field of the material andmore specifically may be in the range of 1 to 5 kV/mm.

The mechanical quality factor Qm of the piezoelectric element can becalculated from the resonance frequency and the antiresonant frequencymeasured with a commercially available impedance analyzer in accordancewith a standard of Japan Electronics and Information TechnologyIndustries Association (JEITA EM-4501). This method is hereinafterreferred to as a resonance-antiresonance method.

The piezoelectric constant of the piezoelectric element can be measuredwith a d₃₃ meter. The resistivity of the piezoelectric element can bemeasured with a semiconductor parameter analyzer. The dielectric loss ofthe piezoelectric element can be measured with the impedance analyzer.

(Multilayered Piezoelectric Element)

A multilayered piezoelectric element manufactured using a piezoelectricmaterial according to an embodiment of the present invention will bedescribed below.

A multilayered piezoelectric element according to an embodiment of thepresent invention includes piezoelectric material layers and electrodelayers alternately stacked on top of one another. The electrode layersinclude an internal electrode. The piezoelectric material layers includea piezoelectric material according to an embodiment of the presentinvention.

FIGS. 2A and 2B are schematic cross-sectional views of a multilayeredpiezoelectric element according to an embodiment of the presentinvention. A multilayered piezoelectric element according to anembodiment of the present invention includes piezoelectric materiallayers 54 and electrode layers including an internal electrode 55. Themultilayered piezoelectric element includes the piezoelectric materiallayers 54 and the layered electrodes alternately stacked on top of oneanother. The piezoelectric material layers 54 are made of thepiezoelectric material described above. The electrodes may includeexternal electrodes, such as a first electrode 51 and a second electrode53, as well as the internal electrode 55.

FIG. 2A illustrates the structure of a multilayered piezoelectricelement according to an embodiment of the present invention. Themultilayered piezoelectric element includes a layered body 56 betweenthe first electrode 51 and the second electrode 53. The layered body 56includes two piezoelectric material layers 54 with the internalelectrode 55 interposed therebetween. The numbers of piezoelectricmaterial layers and internal electrodes are not particularly limited andmay be increased, as illustrated in FIG. 2B. The multilayeredpiezoelectric element illustrated in FIG. 2B includes a layered bodybetween a first electrode 501 and a second electrode 503. The layeredbody includes nine piezoelectric material layers 504 and eight internalelectrodes 505 (505 a and 505 b) alternately stacked on top of oneanother. The multilayered piezoelectric element further includes anexternal electrode 506 a and an external electrode 506 b for connectingthe internal electrodes to each other.

The size and shape of the internal electrodes 55 and 505 and theexternal electrodes 506 a and 506 b may be different from the size andshape of the piezoelectric material layers 54 and 504. Each of theinternal electrodes 55 and 505 and the external electrodes 506 a and 506b may be composed of a plurality of portions.

Each of the internal electrodes 55 and 505, the external electrodes 506a and 506 b, the first electrodes 51 and 501, and the second electrodes53 and 503 is an electrically conductive layer having a thickness in therange of approximately 5 to 2000 nm. The material of each of theelectrodes is not particularly limited and may be any material that iscommonly used for piezoelectric elements. Examples of such a materialinclude metals, such as Ti, Pt, Ta, Ir, Sr, In, Sn, Au, Al, Fe, Cr, Ni,Pd, Ag, and Cu, and compounds thereof. Each of the internal electrodes55 and 505 and the external electrodes 506 a and 506 b may be made ofone of these materials or a mixture or an alloy thereof or may be amultilayer made of two or more of the materials. These electrodes may bemade of different materials. The internal electrodes 55 and 505 maycontain at least one of Ni and Cu, which are inexpensive electrodematerials. When the internal electrodes 55 and 505 contain at least oneof Ni and Cu, the multilayered piezoelectric element may be baked in areducing atmosphere.

The internal electrode 55 and the internal electrodes 505 of themultilayered piezoelectric element may contain Ag and Pd. The weightratio M1/M2 of the weight M1 of Ag to the weight M2 of Pd is preferablyin the range of 1.5≤M1/M2≤9.0, more preferably 2.3M1/M2≤4.0. A weightratio M1/M2 of less than 1.5 is undesirable because of a high sinteringtemperature of the internal electrode(s). A weight ratio M1/M2 of morethan 9.0 is also undesirable because the internal electrode(s) has anisland structure and a heterogeneous surface.

As illustrated in FIG. 2B, the plurality of electrodes including theinternal electrodes 505 may be connected to each other in order tosynchronize the driving voltage phases. For example, the internalelectrodes 505 a may be connected to the first electrode 501 through theexternal electrode 506 a. The internal electrodes 505 b may be connectedto the second electrode 503 through the external electrode 506 b. Theelectrodes may be connected by any method. For example, an electrode oran electric wire for connection may be disposed on a side surface of themultilayered piezoelectric element. Alternatively, a through-holepassing through the piezoelectric material layers 504 may be formed, andthe inside of the through-hole may be coated with an electricallyconductive material to connect the electrodes.

(Liquid Discharge Head)

A liquid discharge head according to an embodiment of the presentinvention includes a liquid chamber and a discharge port incommunication with the liquid chamber. The liquid chamber has avibrating portion that includes a piezoelectric element or amultilayered piezoelectric element according to an embodiment of thepresent invention. A liquid to be discharged from a liquid dischargehead according to an embodiment of the present invention may be anyfluid, for example, an aqueous liquid or a nonaqueous liquid, such aswater, an ink, or a fuel.

FIGS. 3A and 3B are schematic views of a liquid discharge head accordingto an embodiment of the present invention. As illustrated in FIGS. 3Aand 3B, the liquid discharge head includes a piezoelectric element 101according to an embodiment of the present invention. The piezoelectricelement 101 includes a first electrode 1011, a piezoelectric material1012, and a second electrode 1013. The piezoelectric material 1012 maybe patterned, as illustrated in FIG. 3B.

FIG. 3B is a schematic view of the liquid discharge head. The liquiddischarge head includes a discharge port 105, an individual liquidchamber 102, a communicating hole 106 that connects the individualliquid chamber 102 to the discharge port 105, a liquid chamber partitionwall 104, a common liquid chamber 107, a diaphragm 103, and thepiezoelectric element 101. Although the piezoelectric element 101 isrectangular in FIG. 3B, the piezoelectric element 101 may be of anothershape, such as elliptical, circular, or parallelogrammic. In general,the piezoelectric material 1012 has a shape corresponding to the shapeof the individual liquid chamber 102.

The piezoelectric element 101 of the liquid discharge head will bedescribed in detail below with reference to FIG. 3A. FIG. 3A is across-sectional view of FIG. 3B in the width direction of thepiezoelectric element. Although the piezoelectric element 101 has arectangular cross section in FIG. 3A, the piezoelectric element 101 mayhave a trapezoidal or inverted trapezoidal cross section. In FIG. 3A,the first electrode 1011 is a lower electrode, and the second electrode1013 is an upper electrode. The first electrode 1011 and the secondelectrode 1013 may be arranged differently. For example, the firstelectrode 1011 may be a lower electrode or an upper electrode. Likewise,the second electrode 1013 may be an upper electrode or a lowerelectrode. A buffer layer 108 may be disposed between the diaphragm 103and the lower electrode. These different designations result fromvariations in the method for manufacturing the device, and each of thecases has the advantages of the present invention.

In the liquid discharge head, the diaphragm 103 bends upward anddownward with the expansion and contraction of the piezoelectricmaterial 1012, thereby applying pressure to a liquid in the individualliquid chamber 102. This allows the liquid to be discharged from thedischarge port 105. A liquid discharge head according to an embodimentof the present invention can be used in printers and in the manufactureof electronic equipment. The diaphragm 103 has a thickness of 1.0 μm ormore and 15 μm or less, preferably 1.5 μm or more and 8 μm or less. Thematerial of the diaphragm is not particularly limited and may be Si. Siof the diaphragm may be doped with boron or phosphorus. The buffer layerand the electrode on the diaphragm may constitute the diaphragm. Thebuffer layer 108 has a thickness of 5 nm or more and 300 nm or less,preferably 10 nm or more and 200 nm or less. The discharge port 105 hasan equivalent circular diameter of 5 μm or more and 40 μm or less. Thedischarge port 105 may be circular, star-shaped, square, or triangular.

(Liquid Discharge Apparatus)

A liquid discharge apparatus according to an embodiment of the presentinvention will be described below. The liquid discharge apparatusincludes a stage configured to receive an object and the liquiddischarge head.

The liquid discharge apparatus may be an ink jet recording apparatus, asillustrated in FIGS. 4 and 5. FIG. 5 illustrates the liquid dischargeapparatus (ink jet recording apparatus) 881 illustrated in FIG. 4without exteriors 882 to 885 and 887. The ink jet recording apparatus881 includes an automatic feeder 897 for automatically feeding arecording paper sheet as a transfer medium to the main body 896 of theapparatus. The ink jet recording apparatus 881 further includes aconveying unit 899 serving as a stage configured to receive an object,which conveys a recording paper sheet from the automatic feeder 897 to apredetermined recording position and from the recording position to anoutlet 898, a recording unit 891 for recording to the recording paper atthe recording position, and a recovering unit 890 for recovering therecording unit 891. The recording unit 891 includes a carriage 892 forhousing a liquid discharge head according to an embodiment of thepresent invention. The carriage 892 travels along a rail.

In such an ink jet recording apparatus, the carriage 892 travels along arail in response to electric signals sent from a computer. Upon theapplication of a driving voltage to electrodes disposed on apiezoelectric material, the piezoelectric material is deformed. Upon thedeformation, the piezoelectric material presses the individual liquidchamber 102 via the diaphragm 103 illustrated in FIG. 3B, therebydischarging an ink from the discharge port 105 to print characters. Aliquid discharge apparatus according to an embodiment of the presentinvention can uniformly discharge a liquid at a high speed and can bereduced in size.

In addition to the printer described above, a liquid discharge apparatusaccording to an embodiment of the present invention can be used inprinting apparatuses, for example, ink jet recording apparatuses, suchas facsimile machines, multifunction devices, and copying machines,industrial liquid discharge apparatuses, and drawing apparatuses forobjects.

Users can select a desired transfer medium for each application. Theliquid discharge head may move relative to a transfer medium disposed ona stage serving as a mounting portion.

(Ultrasonic Motor)

An ultrasonic motor according to an embodiment of the present inventionincludes a vibrating member and a moving body in contact with thevibrating member. The vibrating member includes a piezoelectric elementor a multilayered piezoelectric element according to an embodiment ofthe present invention.

FIGS. 6A and 6B are schematic views of an ultrasonic motor according toan embodiment of the present invention. The ultrasonic motor illustratedin FIG. 6A includes a single plate of a piezoelectric element accordingto an embodiment of the present invention. The ultrasonic motor includesan oscillator 201, a rotor 202 pressed against a sliding surface of theoscillator 201 by the action of a pressure spring (not shown), and anoutput shaft 203, which is formed integrally with the rotor 202. Theoscillator 201 includes a metal elastic ring 2011, a piezoelectricelement 2012 according to an embodiment of the present invention, and anorganic adhesive 2013 (epoxy or cyanoacrylate) that bonds thepiezoelectric element 2012 to the elastic ring 2011.

Although not shown in the figure, the piezoelectric element 2012includes a piezoelectric material between a first electrode and a secondelectrode. Upon the application of two-phase alternating voltages thatdiffer by an odd number times π/2 in phase to a piezoelectric elementaccording to an embodiment of the present invention, a flexuraltraveling wave occurs in the oscillator 201, and points on the slidingsurface of the oscillator 201 go through elliptical motion. The rotor202 pressed against the sliding surface of the oscillator 201 receivesfriction force from the oscillator 201 and rotates in a directionopposite to the direction of the flexural traveling wave. A body to bedriven (not shown) joined to the output shaft 203 is driven by therotational force of the rotor 202. Upon the application of a voltage toa piezoelectric material, the piezoelectric material expands andcontracts because of the transverse piezoelectric effect. An elasticbody, such as a metal, joined to the piezoelectric element is bent withthe expansion and contraction of the piezoelectric material. Theultrasonic motor described herein utilizes this principle.

FIG. 6B illustrates an ultrasonic motor that includes a multilayeredpiezoelectric element. The oscillator 204 includes a multilayeredpiezoelectric element 2042 in a tubular metal elastic body 2041. Themultilayered piezoelectric element 2042 includes a plurality of layeredpiezoelectric materials (not shown) and includes a first electrode and asecond electrode on the outer surfaces of the layered piezoelectricmaterials and internal electrodes within the layered piezoelectricmaterials. The metal elastic body 2041 is fastened with a bolt to holdthe piezoelectric element 2042, thereby constituting the oscillator 204.Upon the application of alternating voltages of different phases to thepiezoelectric element 2042, the oscillator 204 causes two oscillationsperpendicular to each other. The two oscillations are synthesized toform a circular oscillation for driving the tip of the oscillator 204.The oscillator 204 has an annular groove at its upper portion. Theannular groove increases the oscillatory displacement for driving. Arotor 205 is pressed against the oscillator 204 by the action of apressure spring 206 and receives friction force for driving. The rotor205 is rotatably supported by a bearing.

(Optical Apparatus)

An optical apparatus according to an embodiment of the present inventionwill be described below. The optical apparatus includes a drive unitthat includes the ultrasonic motor described above.

FIGS. 7A and 7B are cross-sectional views of an interchangeable lensbarrel of a single-lens reflex camera, which is an optical apparatusaccording to an embodiment of the present invention. FIG. 8 is anexploded perspective view of an interchangeable lens barrel of asingle-lens reflex camera, which is an optical apparatus according to anembodiment of the present invention. A fixed barrel 712, a linear guidebarrel 713, and a front lens group barrel 714 are fixed to a removablemount 711 of the camera. These components are fixed members of theinterchangeable lens barrel.

The linear guide barrel 713 has a linear guide groove 713 a for a focuslens 702 in the optical axis direction. The focus lens 702 is supportedby a rear lens group barrel 716. Cam rollers 717 a and 717 b protrudingoutwardly in the radial direction are fixed to the rear lens groupbarrel 716 with a screw 718. The cam roller 717 a fits in the linearguide groove 713 a.

A cam ring 715 rotatably fits in the internal circumference of thelinear guide barrel 713. A roller 719 fixed to the cam ring 715 iscaught in an annular groove 713 b of the linear guide barrel 713,thereby restricting the relative displacement of the linear guide barrel713 and the cam ring 715 in the optical axis direction. The cam ring 715has a cam groove 715 a for the focus lens 702. The cam roller 717 b alsofits in the cam groove 715 a.

A rotation transmitting ring 720 is rotatably held by a ball race 727 ata fixed position on the periphery of the fixed barrel 712. A drivenroller 722 is rotatably held by a shaft 720 f extending radially fromthe rotation transmitting ring 720. A large-diameter portion 722 a ofthe driven roller 722 is in contact with a mount side end face 724 b ofa manual focus ring 724. A small-diameter portion 722 b of the drivenroller 722 is in contact with a joint 729. Six driven rollers 722 aredisposed at regular intervals on the periphery of the rotationtransmitting ring 720. Each of the driven rollers 722 satisfies thestructural relationship described above.

A low-friction sheet (washer member) 733 is disposed on the inside ofthe manual focus ring 724. The low-friction sheet 733 is disposedbetween a mount side end face 712 a of the fixed barrel 712 and a frontend face 724 a of the manual focus ring 724. The low-friction sheet 733has a circular outer surface having a diameter that fits to the innerdiameter 724 c of the manual focus ring 724. The inner diameter 724 c ofthe manual focus ring 724 fits to the diameter of an outer portion 712 bof the fixed barrel 712. The low-friction sheet 733 can reduce frictionin the rotating ring mechanism in which the manual focus ring 724rotates about the optical axis relative to the fixed barrel 712.

The large-diameter portion 722 a of the driven roller 722 is pressedagainst the mount side end face 724 b of the manual focus ring 724because the wave washer 726 presses the ultrasonic motor 725 forward tothe front of the lens. Likewise, because the wave washer 726 presses theultrasonic motor 725 forward to the front of the lens, thesmall-diameter portion 722 b of the driven roller 722 is pressed againstthe joint 729. The wave washer 726 is prevented from moving toward themount by a washer 732 bayonet coupled to the fixed barrel 712. Thespring force (impellent force) of the wave washer 726 is transmitted tothe ultrasonic motor 725 and the driven roller 722 and furthermorepresses the manual focus ring 724 against the mount side end face 712 aof the fixed barrel 712. In other words, the manual focus ring 724 ispressed against the mount side end face 712 a of the fixed barrel 712via the low-friction sheet 733.

Thus, when the ultrasonic motor 725 is rotated by a control unit (notshown) relative to the fixed barrel 712, the driven roller 722 rotatesabout the shaft 720 f because the joint 729 is in frictional contactwith the small-diameter portion 722 b of the driven roller 722. Therotation of the driven roller 722 about the shaft 720 f causes therotation of the rotation transmitting ring 720 about the optical axis(automatic focusing).

When a manual input unit (not shown) provides the manual focus ring 724with rotational force about the optical axis, since the mount side endface 724 b of the manual focus ring 724 is pressed against thelarge-diameter portion 722 a of the driven roller 722, the driven roller722 is rotated about the shaft 720 f because of friction force. Therotation of the large-diameter portion 722 a of the driven roller 722about the shaft 720 f causes the rotation of the rotation transmittingring 720 about the optical axis. However, the ultrasonic motor 725 isnot rotated because of the friction force between a rotor 725 c and astator 725 b (manual focusing).

The rotation transmitting ring 720 is provided with two focus keys 728facing each other. These focus keys 728 fit into notches 715 b at thetip of the cam ring 715. Upon automatic focusing or manual focusing, therotation transmitting ring 720 is rotated about the optical axis, andthe rotational force is transmitted to the cam ring 715 via the focuskeys 728. When the cam ring 715 is rotated about the optical axis, thecam roller 717 b moves the cam roller 717 a and the rear group lensbarrel 716 restricted by the linear guide groove 713 a forward orbackward along the cam groove 715 a of the cam ring 715. This drives thefocus lens 702 and allows focusing.

Although an optical apparatus according to an embodiment of the presentinvention has been described with reference to an interchangeable lensbarrel of a single-lens reflex camera, the optical apparatus may also beapplied to optical apparatuses that include an ultrasonic motor in adrive unit, for example, cameras, such as compact cameras, electronicstill cameras, and personal digital assistants including a camera.

(Vibratory Apparatus and Dust Removing Device)

Vibratory apparatuses for conveying or removing particles, powders, anddroplets are widely used in electronic equipment.

As an example of a vibratory apparatus according to the presentinvention, a dust removing device that includes a piezoelectric elementaccording to an embodiment of the present invention will be describedbelow. A vibratory apparatus according to an embodiment of the presentinvention includes a vibrating member that includes the piezoelectricelement or the multilayered piezoelectric element described abovedisposed on a diaphragm. The dust removing device includes a vibratingportion that includes the vibratory apparatus described above.

FIGS. 9A and 9B are schematic views of a dust removing device 310according to an embodiment of the present invention. The dust removingdevice 310 includes a plate of the piezoelectric element 330 and thediaphragm 320. The piezoelectric element 330 may be a multilayeredpiezoelectric element according to an embodiment of the presentinvention. The diaphragm 320 may be made of any material. When the dustremoving device 310 is used in optical devices, the diaphragm 320 may bemade of a translucent or transparent material or a light reflectivematerial.

FIGS. 10A to 10C are schematic views of the piezoelectric element 330illustrated in FIGS. 9A and 9B. FIGS. 10A and 10C illustrate the frontand back sides of the piezoelectric element 330. FIG. 10B is a side viewof the piezoelectric element 330. As illustrated in FIGS. 9A and 9B, thepiezoelectric element 330 includes a piezoelectric material 331, a firstelectrode 332, and a second electrode 333. The first electrode 332 andthe second electrode 333 are disposed on opposite sides of thepiezoelectric material 331. As in FIGS. 9A and 9B, the piezoelectricelement 330 may be a multilayered piezoelectric element according to anembodiment of the present invention. In this case, the piezoelectricmaterial 331 includes piezoelectric material layers and internalelectrodes alternately stacked on top of one another. The internalelectrodes are alternately connected to the first electrode 332 and thesecond electrode 333, thereby allowing the piezoelectric material layersto alternately have a drive waveform of a different phase. Asillustrated in FIG. 10C, a surface of the piezoelectric element 330 onwhich the first electrode 332 is disposed is referred to as a firstelectrode surface 336. As illustrated in FIG. 10A, a surface of thepiezoelectric element 330 on which the second electrode 333 is disposedis referred to as a second electrode surface 337.

The term “electrode surface”, as used herein, refers to a surface of apiezoelectric element on which an electrode is disposed. For example, asillustrated in FIG. 10B, the first electrode 332 may round a corner andextends to the second electrode surface 337.

As illustrated in FIGS. 9A and 9B, the first electrode surface 336 ofthe piezoelectric element 330 is bonded to the diaphragm 320. Actuationof the piezoelectric element 330 produces a stress between thepiezoelectric element 330 and the diaphragm 320, causing out-of-planeoscillations on the diaphragm 320. The dust removing device 310 removesforeign matter, such as dust, on the diaphragm 320 by the action ofout-of-plane oscillations. The term “out-of-plane oscillations”, as usedherein, refers to elastic oscillations that cause displacements of adiaphragm in the optical axis direction or the diaphragm thicknessdirection.

FIGS. 11A and 11B are schematic views illustrating the vibrationprinciple of the dust removing device 310. In FIG. 11A, in-phasealternating voltages are applied to a left-and-right pair of thepiezoelectric elements 330 to cause out-of-plane oscillations of thediaphragm 320. The direction of polarization of the piezoelectricmaterial constituting the left-and-right pair of the piezoelectricelements 330 is the same as the thickness direction of the piezoelectricelements 330. The dust removing device 310 is driven in a seventhoscillation mode. In FIG. 11B, an anti-phase alternating voltage isapplied to a left-and-right pair of the piezoelectric elements 330 tocause out-of-plane oscillations of the diaphragm 320. The dust removingdevice 310 is driven in a sixth oscillation mode. The dust removingdevice 310 can employ at least two oscillation modes to effectivelyremove dust on the surface of the diaphragm.

(Image Pickup Apparatus)

An image pickup apparatus according to an embodiment of the presentinvention will be described below. The image pickup apparatus includesthe dust removing device and an image pickup element unit, wherein thedust removing device includes a diaphragm on the light-receiving surfaceof the image pickup element unit. FIGS. 12 and 13 illustrate a digitalsingle-lens reflex camera, which is an image pickup apparatus accordingto an embodiment of the present invention.

FIG. 12 is a front perspective view of the main body 601 of the cameraviewed from the object side. An imaging lens unit has been removed. FIG.13 is an exploded perspective view of the inside of the camera,illustrating surrounding structures of a dust removing device accordingto an embodiment of the present invention and an image pickup unit 400.

The main body 601 of the camera includes a mirror box 605 to which animage light beam passing through an imaging lens is directed. The mirrorbox 605 includes a main mirror (quick return mirror) 606. The mainmirror 606 can make an angle of 45 degrees with the optical axis todirect an image light beam to a penta roof mirror (not shown) or mayavoid the image light beam in order to direct the image light beam to animage pickup element (not shown).

The mirror box 605 and a shutter unit 200 are disposed in front of amain body chassis 300 of the main body 601 of the camera in this orderfrom the object side. The image pickup unit 400 is disposed on thephotographer side of the main body chassis 300. The image pickup unit400 is installed such that an image pickup surface of the image pickupelement is disposed at a predetermined distance from and parallel to thesurface of a mount 602 to which an imaging lens unit is to be attached.

The image pickup unit 400 includes a vibrating component of a dustremoving device and an image pickup element unit. The vibratingcomponent of the dust removing device is disposed on the same axis asthe light-receiving surface of the image pickup element unit.

Although the digital single-lens reflex camera has been described as animage pickup apparatus according to an embodiment of the presentinvention, the image pickup apparatus may be an interchangeable-lenscamera, such as a mirrorless digital interchangeable-lens camera withoutthe mirror box 605. Among various image pickup apparatuses andelectrical and electronic equipment that include image pickupapparatuses, such as interchangeable-lens video cameras, copyingmachines, facsimile machines, and scanners, an image pickup apparatusaccording to an embodiment of the present invention can particularly beapplied to devices that require the removal of dust deposited on asurface of an optical component.

(Electronic Equipment)

Electronic equipment according to an embodiment of the present inventionwill be described below. The electronic equipment includes apiezoelectric acoustic component that includes a piezoelectric elementor a multilayered piezoelectric element according to an embodiment ofthe present invention. The piezoelectric acoustic component may be aloudspeaker, a buzzer, a microphone, or a surface acoustic wave (SAW)device.

FIG. 14 is a perspective view of the main body 931 of a digital camera,which is electronic equipment according to an embodiment of the presentinvention. An optical device 901, a microphone 914, an electronic flashunit 909, and a fill light unit 916 are disposed on the front surface ofthe main body 931. The microphone 914 is disposed within the main bodyand is indicated by a broken line. An opening for catching externalsound is disposed in front of the microphone 914.

A power switch 933, a loudspeaker 912, a zoom lever 932, and a releasebutton 908 for focusing are disposed on the top surface of the main body931. The loudspeaker 912 is disposed within the main body 931 and isindicated by a broken line. An opening for transmitting sound to theoutside is disposed in front of the loudspeaker 912.

The piezoelectric acoustic component may be used in at least one of themicrophone 914, the loudspeaker 912, and a surface acoustic wave device.

Although the digital camera has been described as electronic equipmentaccording to an embodiment of the present invention, the electronicequipment may also be applied to electronic equipment that includes apiezoelectric acoustic component, such as audio-reproducing devices,audio-recording devices, mobile phones, and information terminals.

As described above, a piezoelectric element and a multilayeredpiezoelectric element according to an embodiment of the presentinvention are suitable for liquid discharge heads, liquid dischargeapparatuses, ultrasonic motors, optical apparatuses, vibratoryapparatuses, dust removing devices, image pickup apparatuses, andelectronic equipment. A liquid discharge head manufactured by using apiezoelectric element or a multilayered piezoelectric element accordingto an embodiment of the present invention can have a nozzle density anda discharge velocity higher than or equal to those of liquid dischargeheads manufactured by using a lead-containing piezoelectric element.

A liquid discharge apparatus manufactured by using a liquid dischargehead according to an embodiment of the present invention can have adischarge velocity and discharge accuracy higher than or equal to thoseof liquid discharge apparatuses manufactured by using a lead-containingpiezoelectric element. An ultrasonic motor manufactured by using apiezoelectric element or a multilayered piezoelectric element accordingto an embodiment of the present invention can have driving force anddurability higher than or equal to those of ultrasonic motorsmanufactured by using a lead-containing piezoelectric element.

An optical apparatus manufactured by using an ultrasonic motor accordingto an embodiment of the present invention can have durability andoperation accuracy higher than or equal to those of optical apparatusesmanufactured by using a lead-containing piezoelectric element.

A vibratory apparatus manufactured by using a piezoelectric element or amultilayered piezoelectric element according to an embodiment of thepresent invention can have vibratory capacity and durability higher thanor equal to those of ultrasonic motors manufactured by using alead-containing piezoelectric element.

A dust removing device manufactured by using a vibratory apparatusaccording to an embodiment of the present invention can have dustremoval efficiency and durability higher than or equal to those of dustremoving devices manufactured by using a lead-containing piezoelectricelement.

An image pickup apparatus manufactured by using a dust removing deviceaccording to an embodiment of the present invention can have a dustremoval function higher than or equal to those of image pickupapparatuses manufactured by using a lead-containing piezoelectricelement.

A piezoelectric acoustic component that includes a piezoelectric elementor a multilayered piezoelectric element according to an embodiment ofthe present invention can be used to provide electronic equipment thathas sound production ability higher than or equal to those of electronicequipment manufactured by using a lead-containing piezoelectric element.

A piezoelectric material according to an embodiment of the presentinvention may be used in ultrasonic transducers, piezoelectricactuators, piezoelectric sensors, and ferroelectric memories, as well asliquid discharge heads and motors.

EXAMPLES

Although a piezoelectric material according to an embodiment of thepresent invention is further described in the following examples, thepresent invention is not limited to these examples.

Examples 1 to 42 and Comparative Examples 1 to 9

Table 1 shows the compositions of piezoelectric materials according toExamples 1 to 42 and sintered bodies according to Comparative Examples 1to 9 of the present invention.

TABLE 1 z w Sample RE x′ x y (mol %) (mol %) Comparative example 1 None0.88 0.86 0.88 0 0 Example 1 La 0.88 0.86 0.88 0.25 0.50 Example 2 La0.88 0.86 0.88 0.75 0.50 Example 3 La 0.88 0.86 0.88 5.00 0.50Comparative example 2 La 0.88 0.86 0.88 6.00 0.50 Comparative example 3La 0.80 0.75 0.80 0.75 0.50 Example 4 La 0.85 0.80 0.85 0.75 0.50Example 5 La 0.88 0.86 0.85 0.75 0.50 Example 6 La 0.95 0.93 0.95 0.750.50 Example 7 La 0.88 0.86 0.88 0.25 0 Example 8 La 0.88 0.86 0.88 0.250.20 Example 9 La 0.88 0.86 0.88 0.25 2.00 Comparative example 4 La 0.970.95 0.97 0.75 0.50 Example 10 Nd 0.88 0.86 0.88 0.25 0.50 Example 11 Nd0.90 0.88 0.90 0.75 0.50 Example 12 Sm 0.88 0.86 0.88 0.25 0.50 Example13 Sm 0.90 0.88 0.90 0.75 0.50 Example 14 Dy 0.88 0.86 0.88 0.25 0.50Example 15 Dy 0.88 0.86 0.88 0.75 0.50 Example 16 Dy 0.88 0.86 0.88 2.000.50 Comparative example 5 Dy 0.88 0.86 0.88 6.00 0.50 Comparativeexample 6 Dy 0.80 0.75 0.80 0.75 0.50 Comparative example 7 None 0.850.80 0.85 0.00 0.00 Example 17 Dy 0.85 0.80 0.85 0.75 0.50 Example 18 Dy0.88 0.86 0.85 0.75 0.50 Example 19 Dy 0.95 0.93 0.95 0.75 0.50 Example20 Dy 0.88 0.86 0.88 0.25 0 Example 21 Dy 0.88 0.86 0.88 0.25 0.20Example 22 Dy 0.88 0.86 0.88 0.25 2.00 Comparative example 8 None 0.900.89 0.90 0.00 0.50 Comparative example 9 Dy 0.97 0.95 0.97 0.75 0.00Example 23 Pr 0.88 0.86 0.88 0.25 0.50 Example 24 Pr 0.90 0.88 0.90 0.750.50 Example 25 Eu 0.88 0.86 0.88 0.25 0.50 Example 26 Eu 0.90 0.88 0.900.75 0.50 Example 27 Gd 0.88 0.86 0.88 0.25 0.50 Example 28 Gd 0.90 0.880.90 0.75 0.50 Example 29 Tb 0.88 0.86 0.88 0.25 0.50 Example 30 Tb 0.900.88 0.90 0.75 0.50 Example 31 Pm 0.88 0.86 0.88 0.25 0.50 Example 32 Pm0.90 0.88 0.90 0.75 0.50 Example 33 Tm 0.88 0.86 0.88 0.25 0.50 Example34 Tm 0.90 0.88 0.90 0.75 0.50 Example 35 Ho 0.88 0.86 0.88 0.25 0.50Example 36 Ho 0.90 0.88 0.90 0.75 0.50 Example 37 Er 0.88 0.86 0.88 0.250.50 Example 38 Er 0.90 0.88 0.90 1.50 0.50 Example 39 Yb 0.88 0.86 0.880.25 0.50 Example 40 Yb 0.90 0.88 0.90 1.50 0.50 Example 41 Lu 0.88 0.860.88 0.25 0.50 Example 42 Lu 0.90 0.88 0.90 1.50 0.50

The raw materials included powders of at least 99% pure sodium niobate(NaNbO₃), 99.95% pure barium carbonate (BaCO₃), at least 99% pure bariumtitanate (BaTiO₃), 99.9% pure copper oxide (Cu(II)O), and 99% puresodium carbonate (Na₂CO₃). A rare earth material represented by RE₂O₃(RE denotes at least one element selected from La, Pr, Nd, Pm, Sm, Eu,Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) was a powder of at least 99% purity.

The raw materials were weighed such that the composition of apiezoelectric material includes a perovskite-type metal oxide having thegeneral formula (1): (Na_(x)Ba_(1-y))(Nb_(y)Ti_(1-y))O₃ (wherein0.80≤x≤0.95, and 0.85≤y≤0.95), a rare-earth element (RE) (0≤z≤5 mol %),and Cu (0≤w≤2 mol %), as indicated by x, y, z, and w in Table 1. The rawpowders were mixed in a ball mill for 12 hours.

More specifically, in Example 1, the raw materials were mixed such thatthe La (z) content corresponded to 0.25 mol % of a perovskite-type metaloxide having the general formula (1): (Na_(x)Ba_(1-y))(Nb_(y)Ti_(1-y))O₃(x=0.86 and y=0.88). The raw material of La was at least 99% pure La₂O₃.The La content of 0.25 mol % in Example 1 means that the weight of La₂O₃was 0.815 g (0.695 g of La) per mol of the perovskite-type metal oxidehaving the general formula (1) (171.75 g). Also in Example 1, the rawmaterials were mixed such that the Cu (w) content corresponded to 0.50mol % of the perovskite-type metal oxide. The raw material of Cu was99.9% pure copper oxide (Cu(II)O). The Cu content of 0.50 mol % inExample 1 means that the weight of copper oxide was 0.398 g (0.317 g ofCu) per mol of the perovskite-type metal oxide having the generalformula (1) (171.75 g).

The mixed powder was calcined in the ambient atmosphere at a temperaturein the range of 900° C. to 1100° C. for 2 to 5 hours. The calcinedpowder was pulverized and was granulated with a PVB binder. The weightof the PVB binder corresponded to 3% by weight of the calcined powder.The granulated powder was charged into a mold and was compressed at apressure of 200 MPa, yielding a compact having a diameter of 17 mm and athickness of approximately 1 mm. The compact was fired in the air at atemperature in the range of 1150° C. to 1300° C. for 2 to 6 hours toyield a sintered body.

The density of the sintered body was measured using Archimedes'principle, and the relative density was calculated. The sintered bodiesof the examples and the comparative examples had a relative density of94% or more. Among the samples according to the present invention, thedensity of the samples containing Cu was 1% to 3% higher than thedensity of the samples having the same composition but not containingCu. The addition of Cu reduced the calcination and firing temperaturesby 50° C. to 100° C.

The sintered body was polished to a thickness of approximately 0.5 mm.The constituent phase and the lattice constant of the polished sinteredbody or a powder of the polished sintered body was determined by X-raydiffraction. The X-ray diffraction showed that the samples weresubstantially composed of a single phase of the perovskite structure.

The composition of the sintered body was analyzed by inductively coupledplasma emission spectroscopy (ICP). Table 1 shows the results as x and yof the general formula (1) and RE (z) and Cu (w). The value x in Table 1represents the molar ratio of Na in the sintered body. The value x′represents the molar ratio of Na in the raw materials.

The value x in Table 1 denotes the molar ratio of Na. In all thesamples, the molar ratio of Na was lower than the predictive value. Theelements other than Na had the expected composition. The molar ratio(x/y) of Na (x) to Nb (y) was in the range of 94% to 98% except forExamples 5 and 18, indicating the deficiency of Na. The Cu content waslow and therefore had a measurement error of ±50% in Table 1. The grainsize of the sintered body was determined through observation with anoptical microscope or an electron microscope.

The sintered body had an average grain size in the range of 2 to 50 μmas measured with an electron microscope.

The distribution of Cu in the sintered body was examined by energydispersive X-ray spectroscopy. Most of added Cu was distributed in grainboundaries, and a small portion of Cu was present in the grains.

In order to examine the electrical characteristics, such as thepiezoelectric property and insulation resistance, piezoelectric elementswere manufactured with the piezoelectric materials according to Examples1 to 42. First, in order to relieve stress in the polished sintered bodyand remove organic substance components on the surface of the polishedsintered body, the polished sintered body was heat-treated in the air ata temperature in the range of 400° C. to 500° C. for 30 minutes. A goldelectrode having a thickness of 400 nm was formed on the front and backsides of the polished sintered body by DC sputtering. A titanium filmhaving a thickness of 30 nm was formed as an adhesion layer between theelectrode and the sintered body. The sintered body having the electrodewas cut to prepare a plate-like piezoelectric element 10 mm in length,2.5 mm in width, and 0.5 mm in thickness.

Resistivity was measured with a semiconductor parameter analyzer. Adirect-current voltage of several tens to a hundred volts was applied toa sample, and the electrical resistance was measured 30 seconds afterthe start of voltage application. Resistivity was calculated from themeasured electrical resistance and the dimensions of the sample. Whenthe resistivity is 30 GΩ·cm or more, preferably 100 GΩ·cm or more, thepiezoelectric material and the piezoelectric element have a satisfactorypractical insulation property.

Polarization treatment was performed before the evaluation of thepiezoelectric property. More specifically, a voltage in the range of 1.5to 5 kV/mm was applied to a sample in an oil bath at 150° C. for 30minutes, and the sample was cooled to room temperature while the voltagewas maintained.

The mechanical quality factor Qm of the plate-like piezoelectric elementwas measured using a resonance-antiresonance method. The piezoelectricconstant (d₃₃) of the sample was measured with a Berlincourt d₃₃ meter.Dielectric loss was measured with an impedance analyzer in anenvironmental test box at −20° C. The measurement frequency was 1 kHz,and the applied alternating voltage was 500 mV. Measurement wasperformed after polarization treatment. The temperature dependence ofthe relative dielectric constant was measured from room temperature. Thechange in relative dielectric constant was measured while a sample wascooled from room temperature to −100° C. and was then heated to 350° C.The Curie temperature was calculated from the maximum relativedielectric constant. The samples had a Curie temperature of 150° C. ormore.

Table 2 shows the evaluation results of the samples.

TABLE 2 Piezoelectric Mechanical quality Resistivity Dielectric Sampleconstant d₃₃ (pC/N) factor Qm (—) (GΩ · cm) loss (%) Comparative example1 145 170 5 1.5 Example 1 151 301 115 0.8 Example 2 140 310 220 0.6Example 3 102 318 291 0.5 Comparative example 2 75 304 230 0.5Comparative example 3 95 291 7 1.1 Example 4 117 300 101 0.6 Example 5108 298 35 0.9 Example 6 101 303 106 0.6 Example 7 125 180 34 0.8Example 8 138 225 119 0.9 Example 9 131 412 330 0.7 Comparative example4 86 306 260 0.6 Example 10 148 287 118 0.8 Example 11 137 295 198 0.6Example 12 150 288 116 0.8 Example 13 136 302 201 0.6 Example 14 149 298113 0.8 Example 15 137 305 212 0.6 Example 16 109 309 288 0.5Comparative example 5 74 298 215 0.5 Comparative example 6 91 274 8 1.2Comparative example 7 92 264 14 1.5 Example 17 114 296 103 0.6 Example18 106 296 34 0.9 Example 19 101 303 106 0.6 Example 20 121 178 35 0.8Example 21 136 214 114 0.9 Example 22 129 407 326 0.7 Comparativeexample 8 92 351 16 1.4 Comparative example 9 84 303 254 0.6 Example 23128 265 121 0.7 Example 24 116 271 198 0.7 Example 25 135 315 118 0.7Example 26 124 298 201 0.6 Example 27 136 301 121 0.7 Example 28 121 277206 0.6 Example 29 125 266 125 0.8 Example 30 120 305 203 0.7 Example 31133 296 114 0.8 Example 32 120 322 199 0.7 Example 33 134 288 118 0.6Example 34 117 314 215 0.6 Example 35 129 275 122 0.5 Example 36 116 302224 0.4 Example 37 132 265 136 0.5 Example 38 108 302 235 0.4 Example 39127 297 141 0.5 Example 40 105 309 248 0.4 Example 41 124 281 142 0.5Example 42 102 306 251 0.4

(Evaluation of Piezoelectric Materials and Piezoelectric ElementsAccording to Examples 1 to 42)

The samples according to Examples 1 to 42 were compared with the samplesaccording to Comparative Examples 1 to 9.

Comparative Example 1, which did not contain a rare-earth element andCu, had a low electrical resistance and a significant dielectric loss.Comparative Example 2, which had a La content of 6 mol %, had apiezoelectric constant d₃₃ of less than 100 pC/N.

Comparative Example 3, which had x as low as 0.75, had a low electricalresistance and a significant dielectric loss.

Comparative Example 4, which had y as large as 0.97, had a piezoelectricconstant d₃₃ of less than 100 pC/N.

Comparative Example 5, which had a Dy content of 6 mol %, had apiezoelectric constant d₃₃ of less than 100 pC/N.

Comparative Example 6, which had x as low as 0.75, had a low electricalresistance and a significant dielectric loss.

Comparative Examples 7 and 8, which contained no rare-earth element, hada low electrical resistance and a significant dielectric loss.

Comparative Example 9, which had y as large as 0.97, had a piezoelectricconstant d₃₃ of less than 100 pC/N.

All the samples according to the examples had a piezoelectric constantd₃₃ of 100 pC/N or more, a resistivity of more than 30 GΩ·cm, and adielectric loss of less than 1.0%. The samples according to the examplesother than Examples 7 and 20, which did not contain Cu, and Examples 5and 18, which had x greater than y, had a resistivity of more than 100GΩ·cm.

Comparison of Examples 7 and 8 shows that the addition of Cu to thepiezoelectric ceramic increased the piezoelectric constant, mechanicalquality factor Qm, and resistivity of the sample.

Example 43

The raw materials corresponding to Example 1 were weighed as describedbelow.

Powders of sodium carbonate (Na₂CO₃), niobium oxide (Nb₂O₅), bariumtitanate (BaTiO₃), lanthanum oxide (La₂O₃), and copper oxide (CuO) wereweighed such that Na, Nb, Ba, Ti, La, and Cu satisfied the compositionof Example 1 described in Table 1. The weighed raw powders were mixed ina ball mill overnight and was calcined at a temperature in the range of1000° C. to 1100° C. to yield a calcined powder. The calcined powder wasmixed with a solvent, a binder (PVB), and a plasticizer (dibutylphthalate) to prepare a slurry. The slurry was formed into a green sheethaving a thickness of 50 μm using a doctor blade method.

An electrically conductive paste for an internal electrode was appliedto the green sheet. The electrically conductive paste was a 70% Ag-30%Pd alloy (Ag/Pd=2.33) paste. Nine of the green sheets to which theelectrically conductive paste had been applied were stacked and werefired at 1150° C. for 5 hours to yield a sintered body. The sinteredbody was cut into a 10 mm×2.5 mm piece. The side surfaces of the piecewere polished. A pair of external electrodes (a first electrode and asecond electrode) for alternately connecting internal electrodes wereformed by Au sputtering. Thus, a multilayered piezoelectric element asillustrated in FIG. 2B was manufactured.

The observation of the internal electrodes of the multilayeredpiezoelectric element showed that the electrode material Ag—Pd and thepiezoelectric material were alternately stacked on top of one another.

Before the evaluation of piezoelectricity, a sample was subjected topolarization treatment. More specifically, the sample was heated to 150°C. in an oil bath. While a voltage of 2 kV/mm was applied between thefirst electrode and the second electrode for 30 minutes, the sample wascooled to room temperature.

The evaluation of the piezoelectricity of the multilayered piezoelectricelement showed that the multilayered piezoelectric element had asatisfactory insulation property and had a satisfactory piezoelectricproperty similar to the piezoelectric material according to Example 1.

Example 44

Powders of sodium niobate (NaNbO₃), barium titanate (BaTiO₃), lanthanumoxide (La₂O₃), and copper oxide (CuO) were weighed such that Na, Nb, Ba,Ti, La, and Cu satisfied the composition of Example 2 described inTable 1. The weighed raw powders were mixed in a ball mill overnight andwas calcined at a temperature in the range of 1000° C. to 1100° C. toyield a calcined powder.

The calcined powder was mixed with a solvent, a binder (PVB), and aplasticizer (dibutyl phthalate) to prepare a slurry. The slurry wasformed into a green sheet having a thickness of 50 μm using a doctorblade method. An electrically conductive paste for an internal electrodewas applied to the green sheet. The electrically conductive paste was aNi paste. Nine of the green sheets to which the electrically conductivepaste had been applied were stacked and were heat-pressed.

The heat-pressed layered body was fired in a tubular furnace. Theheat-pressed layered body was fired to a temperature up to 300° C. inthe ambient atmosphere to remove the binder and was then held at 1200°C. for 5 hours in a reducing atmosphere (H₂:N₂=2:98, an oxygenconcentration of 2×10⁻⁶ Pa). During cooling to room temperature, theoxygen concentration was increased to 30 Pa at a temperature of 1000° C.or less.

The sintered body was cut into a 10 mm×2.5 mm piece. The side surfacesof the piece were polished. A pair of external electrodes (a firstelectrode and a second electrode) for alternately connecting internalelectrodes were formed by Au sputtering. Thus, a multilayeredpiezoelectric element as illustrated in FIG. 2B was manufactured.

The observation of the internal electrodes of the multilayeredpiezoelectric element showed that the electrode material (electrodelayer) Ni and piezoelectric material layers were alternately stacked ontop of one another. An electric field of 2 kV/mm was applied to themultilayered piezoelectric element in an oil bath at 150° C. for 30minutes for polarization treatment. The evaluation of the piezoelectricproperty of the multilayered piezoelectric element showed that themultilayered piezoelectric element had a satisfactory insulationproperty and had a satisfactory piezoelectric property similar to thepiezoelectric element according to Example 2.

Example 45

A liquid discharge head illustrated in FIGS. 3A and 3B was manufacturedusing the piezoelectric element according to Example 14. An ink wasdischarged in response to the input of an electric signal.

Example 46

A liquid discharge apparatus illustrated in FIG. 4 was manufacturedusing the liquid discharge head according to Example 45. An ink wasdischarged and deposited onto a recording medium in response to theinput of an electric signal.

Example 47

An ultrasonic motor illustrated in FIG. 6A was manufactured using thepiezoelectric element according to Example 14. Upon the application ofan alternating voltage, the motor rotated.

Example 48

An optical apparatus illustrated in FIGS. 7A and 7B was manufacturedusing the ultrasonic motor according to Example 47. Upon the applicationof an alternating voltage, automatic focusing was observed.

Example 49

A dust removing device illustrated in FIGS. 9A and 9B was manufacturedusing the piezoelectric element according to Example 14. Upon theapplication of an alternating voltage after plastic beads werescattered, satisfactory dust removing efficiency was observed.

Example 50

An image pickup apparatus illustrated in FIG. 12 was manufactured usingthe dust removing device according to Example 49. Dust on the surface ofthe image pickup unit was satisfactorily removed, and images free ofdust defects were obtained.

Example 51

Liquid discharge heads illustrated in FIGS. 3A and 3B were manufacturedusing the multilayered piezoelectric elements according to Examples 43and 44. An ink was discharged in response to the input of an electricsignal.

Example 52

Liquid discharge apparatuses illustrated in FIG. 4 were manufacturedusing the liquid discharge heads according to Example 51. An ink wasdischarged and deposited onto a recording medium in response to theinput of an electric signal.

Example 53

Ultrasonic motors illustrated in FIG. 6B were manufactured using themultilayered piezoelectric elements according to Examples 43 and 44.Upon the application of an alternating voltage, the motors rotated.

Example 54

Optical apparatuses illustrated in FIGS. 7A and 7B were manufacturedusing the ultrasonic motors according to Example 53. Upon theapplication of an alternating voltage, automatic focusing was observed.

Example 55

Dust removing devices illustrated in FIGS. 9A and 9B were manufacturedusing the multilayered piezoelectric elements according to Examples 43and 44. Upon the application of an alternating voltage after plasticbeads were scattered, satisfactory dust removing efficiency wasobserved.

Example 56

Image pickup apparatuses illustrated in FIG. 12 were manufactured usingthe dust removing devices according to Example 55. Dust on the surfaceof the image pickup unit was satisfactorily removed, and images free ofdust defects were obtained.

Example 57

Electronic equipment illustrated in FIG. 14 was manufactured using themultilayered piezoelectric elements according to Examples 43 and 44.Upon the application of an alternating voltage, a loudspeaker operated.

While the present invention has been described with reference toexemplary embodiments, it is to be understood that the invention is notlimited to the disclosed exemplary embodiments. The scope of thefollowing claims is to be accorded the broadest interpretation so as toencompass all such modifications and equivalent structures andfunctions.

INDUSTRIAL APPLICABILITY

A piezoelectric material according to an embodiment of the presentinvention has satisfactory piezoelectricity even at high environmentaltemperatures. A piezoelectric material according to an embodiment of thepresent invention contains no lead and can reduce the load on theenvironment. Thus, a piezoelectric material according to an embodimentof the present invention can be efficiently used also for apparatusesmanufactured using a large amount of piezoelectric material, such asliquid discharge heads, ultrasonic motors, and dust removing devices.

REFERENCE SIGNS LIST

-   -   1 first electrode    -   2 piezoelectric material portion    -   3 second electrode    -   101 piezoelectric element    -   102 individual liquid chamber    -   103 diaphragm    -   104 liquid chamber partition wall    -   105 discharge port    -   106 communicating hole    -   107 common liquid chamber    -   108 buffer layer    -   1011 first electrode    -   1012 piezoelectric material    -   1013 second electrode    -   201 oscillator    -   202 rotor    -   203 output shaft    -   204 oscillator    -   205 rotor    -   206 spring    -   2011 elastic ring    -   2012 piezoelectric element    -   2013 organic adhesive    -   2041 metal elastic body    -   2042 multilayered piezoelectric element    -   310 dust removing device    -   320 diaphragm    -   330 piezoelectric element    -   331 piezoelectric material    -   332 first electrode    -   333 second electrode    -   336 first electrode surface    -   337 second electrode surface    -   51 first electrode    -   53 second electrode    -   54 piezoelectric material layer    -   55 internal electrode    -   56 layered body    -   501 first electrode    -   503 second electrode    -   504 piezoelectric material layer    -   505 a internal electrode    -   505 b internal electrode    -   506 a external electrode    -   506 b external electrode    -   601 main body of camera    -   602 mount    -   605 mirror box    -   606 main mirror    -   200 shutter unit    -   300 main body chassis    -   400 image pickup unit    -   701 front lens group    -   702 rear lens group    -   711 removable mount    -   712 fixed barrel    -   713 linear guide barrel    -   714 front lens group barrel    -   715 cam ring    -   716 rear lens group barrel    -   717 cam roller    -   718 screw    -   719 roller    -   720 rotation transmitting ring    -   722 driven roller    -   724 manual focus ring    -   725 ultrasonic motor    -   726 wave washer    -   727 ball race    -   728 focus key    -   729 joint member    -   732 washer    -   733 low-friction sheet    -   881 liquid discharge apparatus    -   882 exterior    -   883 exterior    -   884 exterior    -   885 exterior    -   887 exterior    -   890 recovering section    -   891 recording portion    -   892 carriage    -   896 main body of apparatus    -   897 automatic feeder    -   898 outlet    -   899 conveying unit    -   901 optical device    -   908 release button    -   909 electronic flash unit    -   912 loudspeaker    -   914 microphone    -   916 fill light unit    -   931 main body    -   932 zoom lever    -   933 power switch

1. A piezoelectric material, comprising: a perovskite-type metal oxidehaving the following general formula (1); and at least one elementselected from La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, andLu, wherein a content of the element is 0.25 mol % or more and 5 mol %or less of the amount of perovskite-type metal oxide(Na_(x)Ba_(1-y))(Nb_(y)Ti_(1-y))O₃  (1) (wherein x satisfies0.80≤x≤0.95, and y satisfies 0.85≤y≤0.95).
 2. The piezoelectric materialaccording to claim 1, further comprising Cu, wherein the Cu content ismore than 0 mol % and 2 mol % or less of the amount of perovskite-typemetal oxide.
 3. The piezoelectric material according to claim 1, whereinx is smaller than y in the general formula (1).
 4. The piezoelectricmaterial according to claim 1, wherein the at least one element isselected from La, Pr, Pm and Tm.
 5. A piezoelectric element, comprising:an electrode portion; and a piezoelectric material portion, wherein thepiezoelectric material portion includes the piezoelectric materialaccording to claim
 1. 6. A piezoelectric element according to claim 5,wherein the piezoelectric material potion and the electrode potion arealternately stacked each another.
 7. The piezoelectric element accordingto claim 6, wherein the electrode potion contains Ag and Pd, and theweight ratio M1/M2 of the weight M1 of Ag to the weight M2 of Pd is inthe range of 1.5≤M1/M2≤9.0.
 8. The piezoelectric element according toclaim 6, wherein the electrode potion contains at least one of Ni andCu.
 9. A liquid discharge head, comprising: a liquid chamber; and adischarge port in communication with the liquid chamber, wherein theliquid chamber has a vibrating portion that includes the piezoelectricelement according to claim
 5. 10. A liquid discharge apparatus,comprising: a stage configured to receive an object; and the liquiddischarge head according to claim
 8. 11. An ultrasonic motor,comprising: a vibrating member that includes the piezoelectric elementaccording to claim 5; and a moving body in contact with the vibratingmember.
 12. An optical apparatus, comprising a drive unit that includesthe ultrasonic motor according to claim
 11. 13. A vibratory apparatus,comprising a vibrating member that includes the piezoelectric elementaccording to claim 5 on a diaphragm.
 14. A dust removing device,comprising a vibrating portion including the vibratory apparatusaccording to claim
 13. 15. An image pickup apparatus, comprising: thedust removing device according to claim 14; and an image pickup elementunit, wherein the diaphragm of the dust removing device is disposed onthe light-receiving surface side of the image pickup element unit.
 16. Apiezoelectric acoustic component, comprising the piezoelectric elementaccording to claim
 5. 17. Electronic equipment, comprising thepiezoelectric element according to claim 5.